WO2020247515A1 - Additifs destinés à l'amélioration de l'écoulement d'huile - Google Patents

Additifs destinés à l'amélioration de l'écoulement d'huile Download PDF

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Publication number
WO2020247515A1
WO2020247515A1 PCT/US2020/035948 US2020035948W WO2020247515A1 WO 2020247515 A1 WO2020247515 A1 WO 2020247515A1 US 2020035948 W US2020035948 W US 2020035948W WO 2020247515 A1 WO2020247515 A1 WO 2020247515A1
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Prior art keywords
additive
crude oil
heavy crude
oil
naphtha
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PCT/US2020/035948
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English (en)
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Douglas Wilson Swain
Susan Townsend Swain
Kenneth Dean Hammett
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Ewo Solutions Llc
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Publication of WO2020247515A1 publication Critical patent/WO2020247515A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1291—Silicon and boron containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1608—Well defined compounds, e.g. hexane, benzene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/024—Group VIII metals: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0286—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0453—Petroleum or natural waxes, e.g. paraffin waxes, asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel

Definitions

  • the disclosure relates generally to the petroleum industry.
  • the disclosure relates specifically to oil additives.
  • Drag reducing agent most commonly polyacrylamides, aqueous polyethylene oxide (PEO), or cellulose ethers such as carboxymethycellulose.
  • PEO polyethylene oxide
  • cellulose ethers such as carboxymethycellulose.
  • Limiting factors of drag reducing agents include product cost, limiting turbulent flow, pipe-flow pressure gradients, and the possible negative effects at the refinery.
  • compositions and methods that decreases the amount of additive needed to reduce the viscosity of heavy crude oil. Further, it would be advantageous to have a composition and method that decreases the amount of naphtha needed to reduce the viscosity of heavy crude oil. It would also be advantageous to have a composition and method that increase the performance of pyrolysis oil (bio-oil) in heavy crude oil applications. Such a composition could aid in at least one of paraffin and/or asphaltene control, increase of API gravity, and viscosity reduction in heavy crude oil.
  • An embodiment of the disclosure is a heavy crude oil additive comprising a naphtha and a pyrolysis oil.
  • the heavy crude oil additive comprising naphtha and pyrolysis oil reduces viscosity of the heavy crude oil.
  • the heavy crude oil additive comprising naphtha and pyrolysis oil increases the API gravity of the heavy crude oil.
  • the heavy crude oil additive comprising naphtha and pyrolysis oil liquifies paraffin and/or asphaltene in heavy crude oil.
  • An embodiment of the disclosure is a method of preparing a heavy crude oil additive comprising adding naphtha to pyrolysis oil.
  • An embodiment of the disclosure is a pyrolysis oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants.
  • An embodiment of the disclosure is a method of preparing a pyrolysis oil additive for use in reducing the viscosity of a heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil; wherein the pyrolysis oil, the at least one pyrolysis oil additive, and a naphtha are added to heavy crude oil to reduce the viscosity of the heavy crude oil.
  • pyrolysis oil, the at least one pyrolysis oil additive, and the naphtha are added to the heavy crude oil at between 0.1 and 20%.
  • An embodiment of the disclosure is a method of preparing a pyrolysis oil additive for use in increasing API gravity in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil; wherein the pyrolysis oil, the at least one pyrolysis oil additive, and a naphtha are added to the heavy crude oil to increase the API gravity of the heavy crude oil.
  • the pyrolysis oil, the at least one pyrolysis oil additive, and the naphtha are added to the heavy crude oil is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of preparing a pyrolysis oil additive for use in liquifying a substance in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil; wherein the pyrolysis oil, the at least one pyrolysis oil additive, and a naphtha are added to the heavy crude oil to liquify a substance in the heavy crude oil.
  • the pyrolysis oil, the at least one pyrolysis oil additive, and the naphtha are added to the heavy crude oil is added to between 0.1 and 20%.
  • the substance to be liquified is at least one selected from the group comprising paraffin and asphaltene.
  • An embodiment of the disclosure is a heavy crude oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants; a naphtha; and a pyrolysis oil.
  • An embodiment of the disclosure is a method of reducing viscosity of a heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude oil is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of increasing API gravity in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude oil is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of liquifying a substance in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude oil is added to between 0.1 and 20%.
  • the substance is at least one selected from the group comprising paraffin and asphaltene.
  • An embodiment of the disclosure is a pyrolysis oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants; and a naphtha.
  • An embodiment of the disclosure is a heavy crude oil additive comprising a liquid petroleum gas (LPG) and a pyrolysis oil.
  • the heavy crude oil additive comprised of an LPG and pyrolysis oil reduces viscosity of the heavy crude oil.
  • the heavy crude oil additive comprised of LPG and pyrolysis oil increases the API gravity of the heavy crude oil.
  • the heavy crude oil additive comprised of LPG and pyrolysis oil liquifies paraffin and/or asphaltene in heavy crude oil.
  • An embodiment of the disclosure is a pyrolysis oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants; and an LPG.
  • An embodiment of the disclosure is a heavy crude oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants; an LPG; and a pyrolysis oil.
  • An embodiment of the disclosure is a method of reducing viscosity of a heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a LPG to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of increasing API gravity in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a LPG to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of liquifying a substance in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a LPG to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • the substance is at least one selected from the group comprising paraffin and asphaltene.
  • the disclosed heavy crude oil additives comprising pyrolysis oil added to naphtha or LPG can also be blended and injected with field gas.
  • compositions can be further blended and injected with CO2.
  • compositions can be blended and directly injected above the pump or downhole for treatment of production crude.
  • compositions can be blended with liquid natural gas (LNG) and injected above the pump or downhole for the treatment of production crude.
  • LNG liquid natural gas
  • compositions can be blended with diesel fuels.
  • compositions can be blended using fractional oils from the pyrolysis oils.
  • compositions can be blended with zeolite and water soluble electrolyzed/hydrolyzed clinoptilolite fragments and nutraceutical, pharmaceutical, and environmental products based thereon.
  • compositions can be blended with at least one of nanoparticles, zeolite, and markers.
  • the crude oil is bitumen.
  • the disclosed compositions can be blended with distillate.
  • the disclosed compositions can be blended with iron nanoparticles.
  • compositions can be blended with methane, ethane, propane, butane, and combinations thereof.
  • compositions can be blended with kerosene.
  • compositions can be blended with marine bunker fuels.
  • Fig. 1 depicts a graph of kinematic viscosity (centistokes) versus temperature for an additive of an additive of 95% naphtha and 5% pyrolysis oil added to crude oil at a ratio of 4%.
  • Fig. 2 depicts a graph of kinematic viscosity (centistokes) versus temperature for a VM + P (crude oil) naphtha additive was added to the crude oil at a ratio of 8%.
  • Fig. 3 depicts a graph of kinematic viscosity (centistokes) versus temperature for an additive of 3001-5 (95% naptha, 5% tire pyrolysis oil) added to crude oil at a ratio of 8%.
  • Fig. 4 depicts a graph of kinematic viscosity (centistokes) versus temperature for an additive of 3001-10 (90% naptha, 10% tire pyrolysis oil) added to crude oil at a ratio of 8%.
  • Fig. 5 depicts the colloidal instability index of four samples. The samples are CAN 10 (crude oil) (-diamond-); mix crude + naphtha (-square-); mix crude + UltraNaphtha (naphtha + pyrolysis oil) (-triangle-); and mix crude + UltraNaphtha (naphtha + pyrolysis oil) (-x-).
  • Additives can be added to heavy crude oil to achieve at least one of the following: reduce viscosity, increase API gravity, and liquefy substances in the heavy crude oil.
  • pyrolysis oil (bio-oil) and naphtha can be added to heavy crude oil for at least one of these purposes.
  • pyrolysis oil and LPG can be added to heavy crude oil for at least one of these purposes.
  • API gravity measures petroleum compared to water. An API gravity greater than 10 indicates that the petroleum is lighter than water and an API gravity less than 10 indicates that the petroleum is heavier than water. Therefore, API gravity is an inverse measure of a petroleum liquid's density relative to that of water.
  • the additives provide flow improvement. Improvements include but are not limited to * Increased Oil & Gas Production
  • the heavy crude oil additives act as a flow diluent.
  • the additives decrease the amount of diluent required for flow assurance. Therefore, the cost of operation is reduced because of the decrease in the volume of diluent used and the increase of the volume of oil shipped in the pipelines.
  • the additives can be blended to a percentage of the amount of crude to be treated to improve flow assurance. In an embodiment, the additives reduce the amount of diluent required by 40-60%. The additives do not negatively effect on the pipeline seals or O-ring materials.
  • the additives provide solutions to many hydrocarbon, paraffin, and asphaltene based problems.
  • the additives combine a unique blend of surface-active compounds with various solubilization chemistries derived from an environmental waste stream.
  • the additives contain nano-surfactants. Due to their size, the nano-engineered reliquification particles drive the blend of liquefaction chemistries into deposits, providing superior dissolving and reliquification capabilities. Deposits across a vast spectrum, even with minimal flow or agitation, can be dissolved.
  • the additives when applied batch-wise, are pumped as the leader followed by a flush of oil or water down the annulus, or in the case of gas lift wells, pumped down the tubing.
  • An embodiment of the disclosure is a heavy crude oil additive comprising a naphtha and a pyrolysis oil.
  • the heavy crude oil additive comprised of naphtha and pyrolysis oil reduces viscosity of the heavy crude oil.
  • the heavy crude oil additive comprised of naphtha and pyrolysis oil increases the API gravity of the crude oil.
  • the heavy crude oil additive comprised of naphtha and pyrolysis oil liquifies paraffin and/or asphaltene in heavy crude oil.
  • pyrolysis oil is added at a pre-determined percentage into naphtha.
  • the combination of pyrolysis oil and naphtha can be added to heavy crude oil at a fixed percentage.
  • the fixed percentage is between 0.1 and 10%.
  • the addition of the pyrolysis oil and naphtha combination to heavy crude oil can bring the viscosity of the heavy crude oil down to levels that allow the heavy crude oil to be transported through pumps and pipes.
  • the addition of the combination also reduces the need for conventional naphtha (that does not contain pyrolysis oil) use by 20% to 60% while still obtaining similar viscosity levels of the heavy crude oil.
  • Pyrolysis oil is the by-product of pyrolysis, which is the heating of an organic material in the absence of oxygen, which decomposes into combustible gases. These combustible gases are condensed into a liquid called pyrolysis oil, bio-oil, bio-crude, or tire oil.
  • Thermal deoxygenation (TDO) is a non-catalytic process using biomass to produce deoxygenated crude oils. During TDO, decomposition converts neutralized biomass hydrolysate to crude hydrocarbons. In an embodiment, the decomposition occurs in a reactor in the absence of oxygen at a temperature of 450°C or more.
  • the pyrolysis oil is comprised of hundreds of oxygenated, organic compounds including but not limited to carboxylic acids, ketones, aldehydes, furans, and sugars.
  • the pyrolysis is a catalytic process.
  • the catalyst is at least one of natural zeolite, synthetic zeolite (H-SDUSY), AI2O3 and Ca(OH)2.
  • the pyrolysis oil is from rubber, including but not limited to tires, rubber pipe, rubber cable, gum outsoles, telephone wire, and/or submarine cable.
  • other potential feedstocks include switchgrass, alfalfa stems, corn stover, com cobs, barley straw, barley hulls, soybean straw, guayule, chicken litter, wood, and/or shale.
  • the chemical additive blend is a mixture, including but not limited to, at least one of a terpene and/or terpenoid, citrus isolates, and surfactant chemistry.
  • the chemical additive comprises at least one terpenoid, at least one citrus isolate, and at least one surfactant.
  • the chemical additive blend is added to the pyrolysis oil at between 0.1 and 20%.
  • Terpenes are classified by the number of isoprene units in the molecule and include, but are not limited to, the following:
  • Hemiterpenes Consist of a single isoprene unit. Isoprene itself is considered the only hemiterpene, but oxygen-containing derivatives including, but not limited to, prenol and isovaleric acid are hemiterpenoids.
  • monoterpenes and monoterpenoids examples include, but are not limited to, geraniol, terpineol, limonene, myrcene, linalool, or pinene. Iridoids are derived from monoterpenes.
  • Sesquiterpenes Consist of three isoprene units and have the molecular formula C 15 H 24.
  • sesquiterpenes and sesqui terpenoids include, but are not limited to, humulene, farnesenes, and farnesol.
  • Diterpenes Consist of four isoprene units and have the molecular formula C 20 H 32. They are derived from geranylgeranyl pyrophosphate. Examples of diterpenes and diterpenoids include, but are not limited to, cafestol, kahweol, cembrene, and taxadiene.
  • Sesterterpenes Have 25 carbons and five isoprene units.
  • An example includes, but is not limited to, geranylfarnesol.
  • Triterpenes Consist of six isoprene units and have the molecular formula C 30 H 48.
  • Sesquarterpenes Consist of seven isoprene units and have the molecular formula C 35 H 56.
  • Examples include, but are not limited to, ferrugicadiol and tetraprenylcurcumene.
  • Tetraterpenes Consist of eight isoprene units and have the molecular formula C 40 H 64.
  • citrus isolates are extracted from fruit juices and oils from the rind of the fruit.
  • the isolates are extracted from other plants.
  • Isolate sources include, but are not limited to, oranges, grapefruits, tangerines, lemons, limes, myrcene, and pinene.
  • Pinene includes but is not limited to, a-pinene.
  • Non-ionic surfactants include a hydrophilic head group and a hydrophobic tail. Nonionic surfactants do not have a charge on their hydrophilic head group.
  • hydrophilic head groups are available in vesicle-forming surfactants.
  • Various types of non ionic surfactants include ethoxylates, alkoxylates, cocamides, ethoxylated aliphatic alcohols, polyoxyethylene surfactants, carboxylic esters, polyethylene glycol esters, anhydrosorbitol ester and its ethoxylated derivatives, glycol esters of fatty acids, carboxylic amides, monoalkanolamine condensates and polyoxyethylene fatty acid amides.
  • the surfactant has an optimized lipophilic tail.
  • the lipophilic tails of the surfactant ions remain inside the oil because they interact more strongly with oil than with water.
  • the polar "heads" of the surfactant molecules coating the micelle interact more strongly with water, so they form a hydrophilic outer layer that forms a barrier between micelles. This inhibits the oil droplets, the hydrophobic cores of micelles, from merging into fewer, larger droplets ("emulsion breaking") of the micelle.
  • the compounds that coat a micelle are typically amphiphilic in nature, meaning that micelles can be stable either as droplets of aprotic solvents such as oil in water, or as protic solvents such as water in oil. When the droplet is aprotic, it is sometimes known as a reverse micelle.
  • An embodiment of the disclosure is a pyrolysis oil additive comprising at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non ionic surfactants.
  • An embodiment of the disclosure is a heavy crude oil additive comprising a pyrolysis oil; at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants; and a naphtha.
  • the additive to the crude oil is added between 0.1 and 20%. In an embodiment, the additive to the crude oil is added at between about 1 and about 10%. In an embodiment, the additive to the crude oil is added at between about 2 and about 8%. In an embodiment, the additive to the crude oil is added at between about 4 and about 6%. In an embodiment, the additive to the crude oil is added at about 4%.
  • An embodiment of the disclosure is a method of reducing viscosity of a heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to reduce the viscosity of the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of increasing API gravity of heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to increase the API gravity of the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • An embodiment of the disclosure is a method of liquifying a substance in heavy crude oil comprising adding at least one selected from the group comprising a terpene, one or more citrus isolates, and one or more non-ionic surfactants to a pyrolysis oil to form a first additive; adding the first additive to a naphtha to form a second additive; and adding the second additive to the heavy crude oil to liquify a substance in the heavy crude oil.
  • the additive to the heavy crude is added to between 0.1 and 20%.
  • the substance to be liquified is at least one selected from the group comprising paraffin and asphaltene.
  • the overall percentage of naphtha needed to reduce viscosity, increase API, and/or liquify paraffin and/or asphaltene in heavy crude oil is reduced with addition of the additives disclosed herein.
  • Advantages of the additives and methods disclosed herein are reduction of the amount of naphtha required to provide the same viscosity reduction; increase of the amount of pipeline compacity equal to the reduction in the amount of naphtha; providing a degree of control over paraffin and asphaltene precipitation and deposition; pyrolysis oil is compatible with the refinery process and adds British thermal unit (BTU) value; and providing of a degree of corrosion protection for the pipeline.
  • BTU British thermal unit
  • the disclosed heavy crude oil additives comprising pyrolysis oil added to naphtha or LPG can also be blended and injected with field gas.
  • Field gas is natural gas extracted from a production well prior to entering the first stage of processing.
  • field gas means feedstock gas prior to entering a natural gas processing plant.
  • Natural gas liquids are extracted from field gas at the natural gas processing plant.
  • “field gas” means“natural gas” or any derivative thereof, extracted from a production well, storage well, gathering system, pipeline, main or transmission line that is used as fuel to power field equipment.
  • compositions can be further blended and injected with CO 2 .
  • compositions can be blended and directly injected above the pump or downhole for treatment of production crude.
  • compositions can be blended with liquid natural gas (LNG) and injected above the pump or downhole for the treatment of production crude.
  • LNG liquid natural gas
  • the disclosed compositions can be blended with diesel fuels.
  • the disclosed compositions can be blended using fractional oils from the pyrolysis oils.
  • Oil can be separated into different fractions using fractional distillation.
  • a distillation column separates fractions by density and boiling point.
  • examples of fractions are C 1 to C 4 gases, C 5 to C 10 naphthas, C5 to C 10 petrol, C 10 to C 16 kerosenes, C 14 to C 20 diesel oils, C 20 to C 50 lubricating oil, C 20 to C70 fuel oils, and C 70 residue.
  • the disclosed compositions can be blended with zeolite and water soluble electrolyzed/hydrolyzed clinoptilolite fragments.
  • Clinoptilolite is a natural zeolite composed of a microporous arrangement of silica and alumina tetrahedral. Zeolite/clinoptilolite can be used in oil and gas filtration. Zeolite/clinoptilolite can bind heavy metals. See US20170107121. The zeolite/clinoptilolite can be used to absorb a heavy metal toxin.
  • the disclosed compositions can be blended with at least one of nanoparticles, zeolite, and markers.
  • a marker can be used to identify the source of a composition.
  • the crude oil is bitumen.
  • compositions can be blended with a distillate.
  • the disclosed compositions can be blended with taggant. See W02012162701.
  • a taggant can be used to identify the source of a product.
  • the taggant is fluorescent.
  • the taggant can be a Stokes- shifting taggant.
  • a Stokes-shifting taggant absorbs radiation at one wavelength and emits radiation at another wavelength.
  • the taggant is an indocyanine green complex.
  • the disclosed compositions can be blended with iron nanoparticles.
  • compositions can be blended with methane, ethane, propane, butane, and combinations thereof.
  • compositions can be blended with kerosene.
  • compositions can be blended with marine bunker fuels.
  • Figure 3 and Table 3 show kinematic viscosity (centistokes) at three different temperatures for an additive of 3001-5 (95% naptha, 5% tire pyrolysis oil) added to crude oil at a ratio of 8%.
  • Fig. 4 and Table 4 show kinematic viscosity (centistokes) at three different temperatures for an additive of 3001-10 (90% naptha, 10% tire pyrolysis oil) added to crude oil at a ratio of 8%.
  • Fig. 5 depicts the colloidal instability index (CII) of four samples.
  • the samples are CAN 10 (crude oil) (-diamond-); mix crude + naphtha (-square-); mix crude + UltraNaphtha (naphtha+pyrolysis oil) (-triangle-); and mix crude + UltraNaphtha (naphtha+py roly sis oil) (- X-). See Table 6.
  • Table 6 and Figure 5 depict the CII value for the three types of samples. In all cases, the CII value was between 0.7 - 0.9, which represents uncertainty in the stability of asphaltenes. However, 2073-01, 2073-02 and 2073-04 samples the CII value is close to 0.7, becoming these crudes less prone to precipitate asphaltenes. Table 6
  • Table 7 provides the values for API gravity, asphaltene %, and kinematic viscosity among other values. The values are provided for various samples including crude oil; virgin naphtha; product 3001 (naphtha + pyrolysis oil); crude + naphtha; crude + naphtha + pyrolysis oil; and crude + naphtha + pyrolysis oil.
  • Product 3001 is UltraNaphtha (2043-01).
  • Table 8 shows a comparison of the obtained velocities.
  • Table 9 show the viscosity results after over 30 days of decantation.
  • Table 10 shows the results for saturates, aromatics, resins, and asphaltenes after 30 days.
  • Table 8 also shows that viscosity of the mix 2074-04 increase to 4744.9 cSt due the crude content was 85% and the naphtha and UltraNaphtha accounted for 15%.
  • Table 7 also shows that the asphaltenes content for 2073-04 increased around 27% in comparison with 2073-01 and 2073-02, which may be caused to the reduction of naphtha and UltraNaphtha content.
  • Table 6 and Figure 5 depict the CII value for the three types of samples. In all cases, the CII value was between 0.7 - 0.9, which represents uncertainty in the stability of asphaltenes. However, 2073-01, 2073-02 and 2073-04 samples the CII value is close to 0.7, becoming these crudes less prone to precipitate asphaltenes.
  • Table 9 shows viscosity results for the mix 2073-01 and 2073-02 after over 30 days. In contrast with Table 8, both increased by around 474.36 cSt. • If the results from Table 7 are compared with Table 10, the asphaltenes content of the mix 2073-02 only increased by 13.3% and for the mix 2073-01 was 28.4%, after over 30 days.
  • compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this disclosure have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and methods and in the steps or in the sequence of steps of the methods described herein without departing from the concept, spirit and scope of the disclosure. More specifically, it will be apparent that certain agents which are both chemically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the disclosure as defined by the appended claims.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Selon l'invention, l'utilisation d'huile de pyrolyse (communément appelée bio-huile, bio-huile brute ou huile pour pneumatique) en combinaison avec du naphta ou du gaz de pétrole liquéfié (GPL) peut être utilisée pour réduire la viscosité, augmenter la gravité API et/ou liquéfier la paraffine et/ou l'asphaltène dans du pétrole brut lourd à un pourcentage global réduit de naphta. Du terpène, des isolats d'agrumes et/ou des tensioactifs non ioniques peuvent être ajoutés à l'huile de pyrolyse afin de former un additif. L'additif peut être combiné à du naphta ou à du GPL et ajouté à du pétrole brut lourd afin de réduire la viscosité, augmenter la gravité API, et/ou liquéfier la paraffine et/ou l'asphaltène à un pourcentage global réduit de naphta.
PCT/US2020/035948 2019-06-03 2020-06-03 Additifs destinés à l'amélioration de l'écoulement d'huile WO2020247515A1 (fr)

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